1. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. 12.4 Reactions of Alcohols, Thiols, Aldehydes, and Ketones Learning Goal Write balanced chemical equations for the combustion, dehydration, and oxidation of alcohols. Write balanced chemical equations for the oxidation and reduction of thiols, aldehydes, and ketones. A flaming dessert is prepared using heat from the combustion of an alcohol: 2CH 3 —CH 2 —OH(g) + 6O 2 (g)  4CO 2 (g) + 6H 2 O(g) + energy

2. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Dehydration of Alcohols Alcohols undergo dehydration when heated with an acid catalyst the loss of —H and —OH from adjacent carbon atoms, producing an alkene and water H +, heat + H 2 O alcohol alkene

3. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Oxidation and Reduction In organic chemistry, oxidation reactions increase the number of carbon–oxygen bonds by the addition of oxygen or a loss of hydrogen atoms reduction reactions reduce the number of bonds between carbon and oxygen atoms

4. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Oxidation of 1 ° Alcohols Alcohols undergo oxidation, which increases the number of carbon and oxygen bonds. Primary alcohols are oxidized to produce an aldehyde. 1 bond to O 2 bonds to O oxidation 1° alcohol aldehyde

5. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Oxidation of 1 ° Alcohols Aldehydes can further oxidize to produce a carboxylic acid. 2 bonds to O 3 bonds to O oxidation aldehyde carboxylic acid

6. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Oxidation of 2 ° Alcohols Secondary alcohols are oxidized to produce a ketone. To indicate the process of oxidation, [O] is placed over the reaction arrow. 1 bond to O 2 bonds to O [O] 2° alcohol ketone

7. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Oxidation of 3 ° Alcohols Tertiary (3°) alcohols do not readily oxidize because there is no hydrogen atom on the carbon bonded to the —OH group. [O] no product no H to oxidize 3° alcohol

8. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Chemistry Link to Health: Methanol Poisoning Methanol is also known as methyl alcohol highly toxic and found in windshield washer fluid, Sterno, and paint strippers rapidly absorbed and oxidized to formaldehyde and then formic acid [O] [O] methyl alcohol formaldehyde formic acid

9. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Oxidation of Thiols When thiols undergo oxidation, an H atom is lost from each of two —SH groups the product is a disulfide protein in hair is cross-linked by disulfide bonds found in the amino acid cysteine

10. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Ethanol, CH 3 CH 2 OH Ethanol acts as a depressant and kills or disables more people than any other drug consumption can be analyzed by using a breathalyzer is metabolized by a social drinker at a rate of 12–15 mg/dL per hour is metabolized by an alcoholic at a rate of 30 mg/dL per hour

11. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Effect of Alcohol on the Body

12. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Tollens’ Test In Tollens’ test, Tollens’ reagent, which contains Ag +, oxidizes aldehydes but not ketones Ag + is reduced to metallic Ag, which looks like a mirror in the test tube

13. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Benedict’s Test In Benedict’s test, Benedict’s reagent, which contains Cu 2+, reacts with aldehydes that have an adjacent —OH group. When Benedict’s solution containing Cu 2+ (CuSO 4 ) ions is added to this type of aldehyde and heated, a brick-red solid of Cu 2 O forms from the aldehyde. The test is negative with simple aldehydes and ketones.

14. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Benedict’s Test In Benedict’s test, the blue Cu 2+ in Benedict’s solution forms a brick-red solid of Cu 2 O in a positive test for many sugars and aldehydes with adjacent hydroxyl groups.

15. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Reduction of Aldehydes and Ketones In the reduction of organic compounds, aldehydes and ketones are reduced by sodium borohydride (NaBH 4 ) or hydrogen (H 2 ) the number of carbon–oxygen bonds is reduced by the addition of hydrogen or the loss of oxygen a catalyst such as nickel, platinum, or palladium is needed for the addition of hydrogen to the carbonyl group

16. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Reduction of Aldehydes and Ketones Aldehydes reduce to form primary alcohols, and ketones reduce to form secondary alcohols. A catalyst such as nickel, platinum, or palladium is needed for the addition of hydrogen to the carbonyl group.

17. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Study Check Select the product for the oxidation of the following: [O] A. B. C. CO 2 + H 2 O D.

18. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Solution Select the product for the oxidation of the following: [O] The correct answer is B.

19. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Study Check Select the product when CH 3 —CH 2 —CH 2 —OH undergoes each of the following reactions: [O] [O] B. C. 1) 2) CO 2 + H 2 O 3) 4)

20. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Solution Select the product when CH 3 —CH 2 —CH 2 —OH undergoes each of the following reactions: [O] [O] B. C. B. 3) C. 4)

21. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Study Check Give the primary product for the reaction of 2-propanol when it undergoes A. oxidation B. dehydration

22. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Solution = 2-propanol = C 3 H 8 O A. oxidation [O] 2 B. dehydration H +, heat + H 2 O

23. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Study Check Write the structure and name of the organic product when each is mixed with Tollens’ reagent. A. butanal B. acetaldehyde C. ethyl methyl ketone

24. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Solution A. Tollens’ butanal butanoic acid B. Tollens’ acetaldehyde acetic acid C.ethyl methyl ketone + Tollens’= no reaction Ketones are not oxidized by Tollens’ reagent.

25. Chemistry: An Introduction to General, Organic, and Biological Chemistry, Twelfth Edition© 2015 Pearson Education, Inc. Concept Map